Aqueous fungicidal composition and use thereof for combating harmful microorganisms

ABSTRACT

The invention relates to aqueous fungicidal active substance compositions and to their use in the control of harmful microorganisms and in particular in the protection of cellulose-comprising materials, particularly wood, from infection by microorganisms, in particular those harmful fungi which can damage wood or cellulose. 
     The active substance composition according to the invention comprises:
     a) at least one fungicidal organic active substance with a solubility in water of not more than 5 g/l at 25° C./1013 mbar, and   b) a finely-divided polymer with an average particle size, determined by dynamic light scattering, of not more than 300 nm, in which the polymer particles comprise the active substance,
 
the polymer being formed from ethylenically unsaturated monomers M comprising:
       at least 60% by weight, based on the total amount of the monomers M, of at least one neutral monoethylenically unsaturated monomer M1 with a solubility in water of not more than 30 g/l at 25° C., and   up to 40% by weight, based on the total amount of the monomers M, of one or more ethylenically unsaturated monomers M2 other than the monomers M1.

The present application is a 37 C.F.R. §1.53(b) divisional of, andclaims priority to, U.S. application Ser. No. 11/587,052 filed Oct. 20,2006. Application Ser. No. 11/587,052 is the national phase under 35U.S.C. §371 of International Application No. PCT/EP2005/004423, filed onApr. 25, 2005. Priority is also claimed to German application102004020332.6 filed on Apr. 26, 2004. The entire contents of each ofthese applications is hereby incorporated by reference.

The present invention relates to aqueous fungicidal active substancecompositions and to their use in the control of harmful microorganisms,in particular for the protection of cellulose-comprising materials, inparticular wood, from infection by harmful fungi, in particular thoseharmful fungi which may be harmful to wood or cellulose.

It is known that wood and also other cellulose-comprising materials canbe attacked and in extreme cases destroyed by microorganisms and inparticular fungi (subsequently harmful fungi) if they are exposed toenvironmental conditions which promote the growth and the development ofsuch microorganisms. In addition, even if some types of wood have anatural resistance to such an infection, others, in particular types ofsoftwood, are extremely susceptible to an infection (see also EN 350,Part 2). For this reason, wood is frequently treated with woodpreservatives.

Conventional wood preservatives based on tar oils, such as carbolineum,are not very attractive because of their intrinsic smell and theirpotential carcinogenicity. Organic fungicides have on several occasionsbeen proposed as wood preservatives (see E. H. Pommer in Ullmann'sEncyclopedia of Industrial Chemistry on CD Rom, 5th edition, 1997, WileyVCH, Weinheim, Wood preservation, chapter 2.3.1). Since the fungicidalactive substances are usually substances which are insoluble in water,these are frequently formulated for the purposes of wood preservation assolutions in organic solvents. However, the use of solvents isassociated with additional costs and, in addition, is undesirable forindustrial hygiene reasons and for environmental protection reasons.

In plant protection, fungicidal active substances which exhibit only alow solubility in water are frequently formulated in the form of aqueoussuspensions or emulsions. While emulsions usually still comprise organicsolvents, suspensions are usually formulated free from solvents. Theactive substance is present in these suspensions in the form of fineparticles with particle sizes in the micrometer region. If wood is nowtreated with such a suspension, the active substance remains on thesurface of the wood since it, because of the particle size, cannotpenetrate into the pores of the wood. However, this is required ifeffective protection of the wood is to be achieved. In addition, theactive substance is easily washed off the surface by the effects of theweather.

Fungicidal transparent varnishes have also on several occasions beenproposed as wood preservative. In this connection, these are aqueouspainting systems based on aqueous polymer latexes which comprise theactive substance in suspended form. Here again the protection of thewood is not satisfactory since the active substances do not penetrateinto the wood but remain on the surface of the wood.

The proposal has been made on several occasions to formulatewater-insoluble fungicidal active substances in the form of aqueousmicro- or nanoemulsions (see, e.g., WO 02/082900, WO 02/45507 and WO99/65301). In contrast to conventional, usually opaque, macroemulsionsin which the disperse phase exhibits particle sizes clearly of greaterthan 1 μm, the active substances in the clear to opaque micro- ornanoemulsions are present in the finely divided form with particle sizesclearly of less than 1000 nm down to 10 nm or less [see in thisconnection D. J. Shaw, Introduction to Colloid and Surface Chemistry,Butterworths, London, 1986, p. 273]. Admittedly, comparatively largeamounts of emulsifier and of organic solvents are necessary for thepreparation of such micro- or nanoemulsions. Because of the highproportion of emulsifier, the danger exists that the active substancewill be leached out, by the action of water, from the wood or thetreated cellulose-comprising material. On the other hand, solvents areundesirable for industrial hygiene reasons and cost reasons. Inaddition, the water-absorbing capacity of the wood on exposure tomoisture and the equilibrium moisture content on storage in a humidatmosphere are increased, in comparison with untreated wood, by the useof the emulsifiers, which makes the wood more susceptible to infectionby harmful fungi. An additional problem of such microemulsions is theirinstability with regard to demixing. Such a demixing can, for example,occur if the microemulsion becomes depleted in emulsifier because of ahigh affinity of the emulsifier for the wood or a depletion in solventoccurs, which can easily happen in the pressure impregnation.

It is therefore an object of the present invention to provide anaqueous, fungicidally effective, composition of fungicidal activesubstances with low solubility in water, i.e, a solubility in water ofless than 5 g/l, in particular less than 1 g/l, at 25° C./1013 mbar,which is advantageously suitable for the protection ofcellulose-comprising materials, in particular wood, from infection byharmful fungi. The composition should in particular comprise only smallamounts of or no volatile organic compounds, such as organic solvents.In addition, the active substance should not, or not to a significantextent, be leached from the treated materials by the effect of water.Furthermore, the aqueous active substance compositions should exhibit abetter stability than conventional suspensions or microemulsions.

It has been found, surprisingly, that this object is achieved by anaqueous active substance composition in which the fungicidal activesubstance which is insoluble in water or only slightly soluble in wateris present in the polymer particles of a finely divided water-insolublepolymer, the polymer particles of which exhibit a average particle sizeof not more than 300 nm, and in which the polymer is formed from atleast 60% by weight, based on the total amount of the monomers M, of atleast one neutral monoethylenically unsaturated monomer M1 with asolubility in water of not more than 30 g/l at 25° C. and up to 40% byweight, based on the total amount of the monomers M, of one or moreethylenically unsaturated monomers M2 other than the monomers M1.

Consequently, the present invention relates to an aqueous activesubstance composition, comprising:

-   a) at least one fungicidal organic active substance with a    solubility in water of not more than 5 g/l at 25° C./1013 mbar, and-   b) a finely-divided polymer with an average particle size,    determined by dynamic light scattering, of not more than 300 nm, in    which the polymer particles comprise the active substance,    the polymer being formed from ethylenically unsaturated monomers M    comprising:    -   at least 60% by weight, based on the total amount of the        monomers M, of at least one neutral monoethylenically        unsaturated monomer M1 with a solubility in water of not more        than 30 g/l at 25° C., and    -   up to 40% by weight, based on the total amount of the monomers        M, of one or more ethylenically unsaturated monomers M2 other        than the monomers M1.

The compositions according to the invention are stable aqueouspreparations of fungicidal active substances which are insoluble inwater or only slightly soluble in water, which in principle are suitablefor all applications in which it is desired to achieve effectiveprotection from infection by microorganisms, in particular harmfulfungi. In spite of the incorporation of the fungicidal active substancein a polymer matrix, the rate of application of active substancenecessary for effective protection is, surprisingly, not higher and in afew cases even lower than when conventional aqueous active substancepreparations are used.

The present invention also relates to the use of such aqueouscompositions for the control of microorganisms, in particular for thecontrol of harmful fungi. The term “control” comprises, here andsubsequently, the prevention or avoidance of infection bymicroorganisms, in particular harmful fungi and also the destruction ofmicroorganisms, in particular harmful fungi, in infected substrates.

The compositions according to the invention are particularly suitablefor the control of microorganisms, in particular of harmful fungi, inwood and other cellulose materials and in particular for the protectionof these materials from infection by microorganisms, in particularharmful fungi. Hence, a particular embodiment of the invention relatesto the use of such compositions for the protection ofcellulose-comprising materials from infection by microorganisms, inparticular from infection by wood-destroying fungi.

However, the aqueous compositions according to the invention are alsosuitable for other applications in which control of microorganisms, inparticular harmful fungi, is desired, for example in plant protection,for the control of phytotoxic microorganisms, in seed treatment, andalso in the protection of materials, as in-can and film preservatives,for antifouling, and for the protection of leather and other organicmaterials from infection by harmful microorganisms.

The particle sizes of the finely divided polymer given here areweight-average particle sizes, as can be determined by dynamic lightscattering. Methods for this are familiar to a person skilled in theart, for example from H. Wiese in D. Distler, WässrigePolymerdispersionen [Aqueous Polymer Dispersions], Wiley-VCH, 1999,chapter 4.2.1, p. 40ff and the literature cited therein, and also H.Auweter, D. Horn, J. Colloid Interf. Sci., 105 (1985), 399, D. Lilge, D.Horn, Colloid Polym. Sci., 269 (1991), 704, or H. Wiese, D. Horn, J.Chem, Phys., 94 (1991), 6429. The average particle size preferablyranges from 10 to 250 nm, in particular from 20 to 200 nm, particularlypreferably from 30 to 150 nm and very particularly preferably from 30 to100 nm.

The polymer is, according to the invention, at least 60% by weight,based on the total amount of the monomers M forming the polymer,preferably 60 to 99.5% by weight and particularly preferably 70 to 99%by weight formed from neutral monoethylenically unsaturated monomers M1with a solubility in water of not more than 30 g/l at 25° C./1013 mbar.In particular, the solubility in water of the monomers M1 under theseconditions is from 0.1 to 20 g/l. Suitable monomers M1 comprisevinylaromatic monomers, such as styrene, esters of monoethylenicallyunsaturated mono- and dicarboxylic acids with 3 to 8 and in particular 3or 4 carbon atoms with C₁-C₁₀-alkanols or with C₅-C₈-cycloalkanols, inparticular the esters of acrylic acid, of methacrylic acid or ofcrotonic acid, the diesters of maleic acid, of fumaric acid and ofitaconic acid, and particularly preferably the esters of acrylic acidwith C₂-C₁₀-alkanols (═C₂-C₁₀-alkyl acrylates), such as ethyl acrylate,n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexylacrylate, 2-ethylhexyl acrylate and 3-propylheptyl acrylate, and theesters of methacrylic acid with C₁-C₁₀-alkanols, such as methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, isobutylmethacrylate, tert-butyl methacrylate, n-hexyl methacrylate and thelike. Suitable monomers M1 are, in addition, vinyl and allyl esters ofaliphatic carboxylic acids with 2 to 10 carbon atoms, for example vinylacetate, vinyl propionate and the vinyl esters of Versatic® acids (vinylversatate), vinyl halides, such as vinyl chloride and vinylidenechloride, conjugated diolefins, such as butadiene and isoprene, andC₂-C₆-olefins, such as ethylene, propene, 1-butene and n-hexene.Preferred monomers M1 are vinylaromatic monomers, in particular styrene,C₂-C₁₀-alkyl acrylates, in particular C₂-C₈-alkyl acrylates, andC₁-C₁₀-alkyl methacrylates.

The ethylenically unsaturated monomers M which form the polymeradvantageously also comprise at least 0.5 to 40% by weight, inparticular 1 to 30% by weight, of at least one ethylenically unsaturatedmonomer M2 other than the monomers M1.

The monomers M2 include in particular monoethylenically unsaturatedmonomers M2a exhibiting at least one acid group or at least one anionicgroup, in particular monomers M2a exhibiting a sulfonic acid group, aphosphonic acid group or one or two carboxylic acid groups, and thesalts of the monomers M2a, in particular the alkali metal salts, e.g.the sodium or potassium salts, and the ammonium salts. These includeethylenically unsaturated sulfonic acids, in particular vinylsulfonicacid, 2-acrylamido-2-methylpropanesulfonic acid,2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid,3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonicacid and their salts, ethylenically unsaturated phosphonic acids, suchas vinylphosphonic acid and vinylphosphonic acid dimethyl ester andtheir salts, and α,β-ethylenically unsaturated C₃-C₈-mono- andC₄-C₈-dicarboxylic acids, in particular acrylic acid, methacrylic acid,crotonic acid, maleic acid, fumaric acid and itaconic acid. Theproportion of the monomers M2a will commonly come to not more than 35%by weight, preferably not more than 20% by weight, e.g. 0.1 to 20% byweight and in particular 0.5 to 15% by weight, based on the total amountof the monomers M.

The monomers M2 additionally include monoethylenically unsaturatedneutral monomers M2b exhibiting a solubility in water of at least 50 g/lat 25° C. and in particular of at least 100 g/l at 25° C. Examples ofthese are the amides of the above-mentioned ethylenically unsaturatedcarboxylic acids, in particular acrylamide and methacrylamide,ethylenically unsaturated nitriles, such as methacrylonitrile andacrylonitrile, hydroxyalkyl esters of the abovementionedα,β-ethylenically unsaturated C₃-C₈-monocarboxylic acids andC₄-C₈-dicarboxylic acids, in particular hydroxyethyl acrylate,hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, and 2- and3-hydroxypropyl methacrylate, and esters of the abovementionedmonoethylenically unsaturated mono- and dicarboxylic acids withC₂-C₄-polyalkylene glycols, in particular the esters of these carboxylicacids with polyethylene glycol or alkylpolyethylene glycols, the(alkyl)polyethylene glycol residue usually exhibiting a molecular weightranging from 100 to 3000. The monomers M2b furthermore includeN-vinylamides, such as N-vinylformamide, N-vinylpyrrolidone,N-vinylimidazole and N-vinylcaprolactam. The proportion of the monomersM2b will preferably come to not more than 20% and in particular not morethan 10% by weight, e.g. 0.1 to 10 and in particular 0.5 to 5% byweight, based on the total amount of the monomers M.

The monomers M2 furthermore include monoethylenically unsaturatedmonomers M2c exhibiting at least one cationic group and/or at least onegroup which can be protonated in the aqueous medium. The monomers M2cinclude in particular those exhibiting a protonatable amino group, aquaternary ammonium group, a protonatable imino group or a quaternizedimino group. Examples of monomers with a protonatable imino group areN-vinylimidazole and vinylpyridines. Examples of monomers with aquaternized imino group are N-alkylvinylpyridinium salts andN-Alkyl-N′-vinylimidazolinium salts, such asN-methyl-N′-vinylimidazolinium chloride or methyl sulfate. Preference isgiven, among the monomers M2c, in particular to the monomers of thegeneral formula (I)

in which

-   R¹ is hydrogen or C₁-C₄-alkyl, in particular hydrogen or methyl,-   R² and R³ are, independently of one another, C₁-C₄-alkyl, in    particular methyl, and-   R⁴ is hydrogen or C₁-C₄-alkyl, in particular hydrogen or methyl,-   Y is oxygen, NH or NR⁵ with R⁵=C₁-C₄-alkyl,-   A is C₂-C₈-alkylene, e.g. 1,2-ethanediyl, 1,2- or 1,3-propanediyl,    1,4-butanediyl or 2-methyl-1,2-propanediyl, if appropriate    interrupted by 1, 2 or 3 nonadjacent oxygen atoms, and-   X⁻ is an anion equivalent, e.g. Cl⁻, HSO₄ ⁻, ½SO₄ ²⁻ or CH₃OSO₃ ⁻,    and the like,    and, for R⁴═H, the free bases of the monomers of the formula I.

Examples of such monomers are 2-(N,N-dimethylamino)ethyl acrylate,2-(N,N-dimethylamino)ethyl methacrylate,2-(N,N-dimethylamino)ethylacrylamide,3-(N,N-dimethylamino)propylacrylamide,3-(N,N-dimethylamino)propylmethacrylamide,2-(N,N-dimethylamino)ethylmethacrylamide,2-(N,N,N-trimethylammonio)ethyl acrylate chloride,2-(N,N,N-trimethylammonio)ethyl methacrylate chloride,2-(N,N,N-trimethylammonio)ethylmethacrylamide chloride,3-(N,N,N-trimethylammonio)propylacrylamide chloride,3-(N,N,N-trimethylammonio)propylmethacrylamide chloride,2-(N,N,N-trimethylammonio)ethylacrylamide chloride, and thecorresponding sulfates and methyl sulfates.

In a preferred embodiment, the monomers M which form the polymercomprise at least one monomer M2c. The proportion of the monomers M2c isthen advantageously 0.1 to 20% by weight, in particular 0.5 to 10% byweight and particularly preferably 1 to 7% by weight, based on the totalamount of the monomers M.

In a particularly preferred embodiment of the invention, the polymerexhibits a net cationic charge, i.e. the molar proportion of themonomers M2c is greater than the molar proportion of the monomers M2a inthe polymer and is preferably 110 mol %, in particular at least 120 mol% and particularly preferably at least 150 mol %, based on the monomersM2a.

The monomers M2 furthermore include all monomers which canconventionally be used in an emulsion polymerization. However, theproportion of monomers exhibiting two or more nonconjugatedethylenically unsaturated double bonds usually comes to not more than 5%by weight, in particular not more than 2% by weight, e.g. 0.01 to 2% byweight and in particular 0.05 to 1.5% by weight, based on the totalamount of monomers.

Furthermore, it has proved to be advantageous for the polymer present inthe compositions according to the invention to exhibit a glasstransition temperature T_(g) of at least 10° C., preferably of at least20° C. and in particular of at least 30° C. In particular, the glasstransition temperature will not exceed a value of 180° C. andparticularly preferably 130° C. If the active substance compositionaccording to the invention comprises several polymers with differentglass transition temperatures, be it in the form of step or core/shellpolymers or in the form of blends of different polymers, the proportionof polymers with a glass transition temperature of at least 10° C.,preferably at least 20° C. and in particular at least 30° C. is at least40% by weight.

The term “glass transition temperature T_(g)” is to be understood hereas the midpoint temperature determined by differential scanningcalorimetry (DSC) according to ASTM D 3418-82 (cf. Ullmann'sEncyclopedia of Industrial Chemistry, 5th edition, volume A 21, VCH,Weinheim, 1992, p. 169, and Zosel, Farbe and Lack, 82 (1976), p.125-134, see also DIN 53765).

In this connection, it proves to be helpful to estimate the glasstransition temperature T_(g) of the copolymer P. According to Fox (T. G.Fox, Bull. Am. Phys. Soc. (Ser. II), 1, 123 [1956] and Ullmann'sEncyclopedia of Industrial Chemistry, Weinheim (1980), p. 17-18), thefollowing equation

$\frac{1}{T_{g}} = {\frac{X^{1}}{T_{g}^{1}} + \frac{X^{2}}{T_{g}^{2}} + {\ldots \mspace{14mu} \frac{X^{n}}{T_{g}^{n}}}}$

is, to a good approximation, valid for the glass transition temperatureof weakly crosslinked copolymers with high molar masses, in whichequation X¹, X², . . . , X^(n) represent the mass fractions of themonomers 1, 2, . . . , n and T_(g) ¹, T_(g) ², . . . , T_(g) ^(n)represent, in degrees Kelvin, the glass transition temperatures of thepolymers formed in each case only from one of the monomers 1, 2, . . . ,n. The latter are, e.g., known from Ullmann's Encyclopedia of IndustrialChemistry, VCH, Weinheim, Vol. A 21, (1992) p, 169, or from J. Brandrup,E. H. Immergut, Polymer Handbook, 3rd ed., J. Wiley, New York, 1989.

All organic substances with low solubility in water which inhibit thegrowth or the propagation of harmful fungi or which destroy the latterare suitable in principle as active substances. Their solubility inwater at 25° C./1013 mbar is generally not more than 5 g/l, frequentlynot more than 3 g/l and in particular not more than 1 g/l, e.g. 0.001g/l to 1 g/l, in particular 0.002 to 0.5 g/l, at 25° C./1013 mbar.

Examples of suitable active substances are the compounds listed asfungicides in the Compendium of Pesticide Common Names:http://www.hclrss.demon.co.uk/class-fungicides.html (Index of commonnames). These include, for example:

-   -   acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl;    -   morpholine compounds, such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine        or tridemorph;    -   anilinopyrimidines, such as pyrimethanil, mepanipyrim or        cyprodinil;    -   antibiotics, such as cycloheximide, griseofulvin, kasugamycin,        natamycin, polyoxin or streptomycin;    -   azoles, such as azaconazoie, bitertanol, bromoconazole,        cyproconazole, diclobutrazoi, difenoconazole, diniconazole,        epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,        flutriafol, ketoconazole, hexaconazole, imazalil, metconazole,        myclobutanil, penconazole, propiconazole, prochloraz,        prothioconazole, tebuconazole, tetraconazole, triadimefon,        triadimenol, triflumizole or triticonazole;    -   dicarboximides, such as iprodione, myclozolin, procymidone or        vinclozolin;    -   dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram or zineb;    -   heterocyclic compounds, such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadone, fenamidone, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,        silthiofam, thiabendazole, thifluzamide, thiophanate-methyl,        tiadinil, tricyclazole or triforine;    -   nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton        or nitrothal-isopropyl;    -   phenylpyrroles, such as fenpiclonil or fludioxonil;    -   strobilurins, such as dimoxystrobin, fluoxastrobin,        kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,        pyraclostrobin and trifloxystrobin;    -   other fungicides, such as acibenzolar-S-methyl, benzoylbenzoate,        dodecylguanidine hydrochloride, benthiavalicarb, carpropamid,        chlorothalonil, cyflufenamid, cymoxanil, diclomezine,        diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid,        fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl,        fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone,        pencycuron, propamocarb, phthalide, tolclofos-methyl, quintozene        or zoxamide;    -   sulfenic acid derivatives, such as captafol, captan,        dichlofluanid, folpet or tolylfluanid;    -   cinnamamides and analogous compounds, such as dimethomorph,        flumetover or flumorph.

These furthermore include:

-   -   iodine compounds, such as diiodomethyl p-tolyl sulfone,        3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal,        3-bromo-2,3-diiodo-3-propenyl ethyl carbonate,        2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl        alcohol, 3-iodo-2-propynyl n-butylcarbamate, 3-iodo-2-propynyl        n-hexylcarbamate, 3-iodo-2-propynyl phenylcarbamate,        O-1-(6-iodo-3-oxohex-5-ynyl) butylcarbamate,        O-1-(6-iodo-3-oxohex-5-ynyl)phenylcarbamate or napcocide;    -   phenol derivatives, such as tribromophenol, tetrachlorophenol,        3-methyl-4-chlorophenol, dichlorophen, o-phenylphenol,        m-phenylphenol or 2-benzyl-4-chlorophenol;    -   isothiazolinones, such as N-methylisothiazolin-3-one,        5-chloro-N-methyl-isothiazolin-3-one,        4,5-dichloro-N-octylisothiazolin-3-one or        N-octylisothiazolin-3-one;    -   (benz)isothiazolinones, such as 1,2-benzisothiazol-3(2H)-one,        4,5-trimethylisothiazol-3-one or 2-octyl-2H-isothiazol-3-one;    -   pyridines, such as 1-hydroxy-2-pyridinethione (and its Na, Fe,        Mn and Zn salts), or tetrachloro-4-methylsulfonylpyridine;    -   metal soaps, such as tin, copper or zinc naphthenate, octoate,        2-ethylhexanoate, oleate, phosphate or benzoate;    -   organotin compounds, e.g. tributyltin (TBT) compounds, such as        tributyltin and tributyl(mononaphthenoyloxy)tin derivatives;    -   dialkyldithiocarbamates and the Na and Zn salts of        dialkyldithiocarbamates, tetramethylthiouram disulfide;    -   nitriles, such as 2,4,5,6-tertrachloroisophthalodinitrile;    -   benzthiazoles, such as 2-mercaptobenzothiazole;    -   quinolines, such as 8-hydroxyquinoline, and their Cu salts;    -   tris-(N-cyclohexyldiazeniumdioxy)aluminum,        (N-cyclohexyldiazeniumdioxy)-tributyltin, or        bis(N-cyclohexyldiazeniumdioxy)copper;    -   3-benzo[b]thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide        (bethoxazin).

With regard to the use of the compositions according to the inventionfor the protection of cellulose-comprising materials from infection bymicroorganisms of relevance in wood preservation, mainly molds,wood-discoloring fungi and wood-destroying fungi, preference is given inparticular to those fungicides which are effective, for example, againstthe following groups of microorganisms:

Wood-Discoloring Fungi:

-   -   ascomycetes, such as Ophiostoma sp. (e.g. Ophiostoma piceae,        Ophiostoma piliferum), Ceratocystis sp. (e.g, Ceratocystis        coerulescens), Aureobasidium pullulans or Sclerophoma sp. (e.g.        Sclerophoma pityophila);    -   deuteromycetes, such as Aspergillus sp. (e.g. Aspergillus        niger), Cladosporium sp. (e.g. Cladosporium sphaerospermum),        Penicillium sp. (e.g. Penicillium funiculosum), Trichoderma sp.        (e.g, Trichoderma viride), Alternaria sp. (e.g. Alternaria        alternata) or Paecilomyces sp. (e.g. Paecilomyces variotii);    -   zygomycetes, such as Mucor sp. (e.g. Mucor hiemalis);

Wood-Destroying Fungi:

-   -   ascomycetes, such as Chaetomium sp. (e.g. Chaetomium globosum),        Humicola sp. (e.g. Humicola grisea), Petriella sp. (e.g.        Petriella setifera) or Trichurus sp. (e.g. Trichurus spiralis);    -   basidiomycetes, such as Coniophora sp. (e.g. Coniophora        puteana), Coriolus sp. (e.g. Coriolus versicolor), Gloeophyllum        sp. (e.g. Gloeophyllum trabeum), Lentinus sp. (e.g. Lentinus        lepideus), Pleurotus sp. (e.g. Pleurotus ostreatus), Poria sp.        (e.g. Poria placenta, Poria vaillantii), Serpula sp. (e.g.        Serpula lacrymans) and Tyromyces sp. (e.g. Tyromyces palustris),

Preferred active substances are hence selected from the group of theconazoles, the group of the morpholines, the group of the strobilurins,the group of the thiazoles, the group of the sulfenamides and the groupof the iodine compounds.

Preference is given in particular to those fungicides mentioned incategory 08 (wood preservatives) in the biocide regulation of theEuropean Union (COMMISSION REGULATION (EC) No. 2032/2003 of Nov. 4,2003).

The aqueous active substance preparations according to the inventioncomprise the fungicidal active substance generally in an amount of 0.1to 50% by weight, preferably in an amount of 0.2 to 30% by weight and inparticular in an amount of 0.5 to 20% by weight, based on the polymerpresent in the composition or based on the total amount of the monomersM used to prepare the polymer.

In addition to the fungicidal active substance, the compositionsaccording to the invention can also comprise one or more insecticidalactive substances. In a preferred embodiment, the insecticidal activesubstances, together with the at least one fungicidal active substance,are present in the polymer particles. The insecticidal active substanceis then preferably an organic active substance with a low solubility inwater generally of not more than 5 g/l, preferably not more than 3 g/land in particular not more than 1 g/l, e.g. 0.001 to 1 g/l or 0.002 to0.5 g/l, at 25° C./1013 mbar. Examples of suitable insecticidal activesubstances are the compounds listed as insecticides in the Compendium ofPesticide Common Names:http://www.hclrss.demon.co.uk/class-insecticides.html (Index of commonnames). These include, for example:

-   -   organo(thio)phosphates, such as acephate, azamethiphos,        azinphos-methyl, chlorpyrifos, chlorpyriphos-methyl,        chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate,        disulfoton, ethion, fenitrothion, fenthion, isoxathion,        malathion, methamidophos, methidathion, methyl-parathion,        mevinphos, monocrotophos, oxydemeton-methyl, paraoxon,        parathion, phenthoate, phosalone, phosmet, phosphamidon,        phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos,        sulprophos, triazophos or trichlorfon;    -   carbamates, such as alanycarb, benfuracarb, bendiocarb,        carbaryl, carbosulfan, fenoxycarb, furathiocarb, indoxacarb,        methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb        or triazamate;    -   pyrethroids, such as allethrin, bifenthrin, cyfluthrin,        cyphenothrin, cypermethrin, and the alpha-, beta-, theta- and        zeta-isomers, deltamethrin, esfenvalerate, ethofenprox,        fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin,        imiprothrin, permethrin, prallethrin, pyrethrin I, pyrethrin II,        silafluofen, tau-fluvalinate, tefluthrin, tetramethrin,        tralomethrin, transfluthrin or zeta-cypermethrin;    -   arthropod growth regulators, such as a) chitin synthesis        inhibitors; e.g. benzoylureas, such as chlorfluazuron,        cyromacin, diflubenzuron, flucycloxuron, flufenoxuron,        hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron;        buprofezin, diofenolan, hexythiazox, etoxazole or        clofentezine; b) ecdysone antagonists, such as halofenozide,        methoxyfenozide or tebufenozide; c) juvenoids, such as        pyriproxyfen, methoprene or fenoxycarb; d) lipid biosynthesis        inhibitors, such as spirodiclofen;    -   neonicotinoids, such as flonicamid, clothianidin, dinotefuran,        imidacloprid, thiamethoxam, nitenpyram, nithiazine, acetamiprid        or thiacloprid;    -   pyrazole insecticides, such as acetoprole, ethiprole, fipronil,        tebufenpyrad, tolfenpyrad and vaniliprole.    -   in addition, abamectin, acequinocyl, amitraz, azadirachtin,        bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazine,        diafenthiuron, diofenolan, emamectin, endosulfan, fenazaquin,        formetanate, formetanate hydrochloride, hydramethylnon,        indoxacarb, piperonyl butoxide, pyridaben, pymetrozine,        spinosad, thiamethoxam, thiocyclam, pyridalyl, fluacyprim,        milbemectin, spiro-mesifen, flupyrazofos, NCS 12, flubendiamide,        bistrifluoron, benclothiaz, pyrafluprole, pyriprole,        amidoflumet, flufenerim, cyflumetofen, lepimectin, profluthrin,        dimefluthrin and metaflumizone.

Preference is given, among these, to those insecticides which areeffective against wood-destroying insects and in particular against thefollowing wood-destroying insects:

Order Coleoptera (Beetles):

-   -   Cerambycidae, such as Hylotrupes bajulus or Callidium violaceum;    -   Lyctidae, such as Lyctus linearis or Lyctus brunneus;    -   Bostrichidae, such as Dinoderus minutus;    -   Anobiidae, such as Anobium punctatum or Xestobium rufovillosum;    -   Lymexylidae, such as Lymexylon navale;    -   Platypodidae, such as Platypus cylindrus;    -   Oedemeridae, such as Nacerda melanura;

Order Hymenoptera(Hymenopterans):

-   -   Formicidae, such as Camponotus abdominalis, Lasius flavus,        Lasius brunneus or Lasius fuliginosus;

Order Isoptera(Termites):

-   -   Kalotermitidae, such as Kalotermes flavicollis or Cryptothermes        brevis;    -   Hodotermitidae, such as Zootermopsis angusticollis or        Zootermopsis nevadensis;    -   Rhinotermitidae, such as Reticulitermes flavipes, Reticulitermes        lucifugus, Coptotermes formosanus or Coptotermes acinaciformis;    -   Mastotermitidae, such as Mastotermes darwiniensis.

These include in particular the insecticidal active substances from theclass of the pyrethroids, arthropod growth regulators, such as chitinbiosynthesis inhibitors, ecdysone antagonists, juvenoids or lipidbiosynthesis inhibitors, neonicotinoids, pyrazole insecticides andchlorfenapyr.

Preference is given in particular to those insecticidal activesubstances mentioned in category 08 (wood preservatives) and category 18(insecticides, acaricides and products to control other arthropods) inthe biocide regulation of the European Union (COMMISSION REGULATION (EC)No. 2032/2003 of Nov. 4, 2003).

The insecticidal active substance is, if desired, usually present in theactive substance composition according to the invention in an amount of0.1 to 50% by weight, preferably in an amount of 0.2 to 30% by weightand in particular in an amount of 0.5 to 20% by weight, based on themonomers M which form the polymer.

The total amount of active substance in the polymer of the compositionsaccording to the invention is preferably 0.2 to 50% by weight, inparticular 0.5 to 30% by weight and particularly preferably 1 to 20% byweight, based on the polymer or on the monomers M which form thepolymer.

The aqueous compositions according to the invention usually comprisesurface-active substances in order to stabilize the polymer particles inthe aqueous medium. These include both protective colloids andlow-molecular-weight emulsifiers, the latter, in contrast to theprotective colloids, generally exhibiting a molecular weight of lessthan 2000 g/mol, in particular of less than 1000 g/mol (weight-average).The protective colloids and emuisfiers can be both cationic, anionic orneutral in nature and zwitterionic in nature.

Examples of anionic surface-active substances are anionic emulsifiers,such as alkylphenylsulfonates, phenylsulfonates, alkyl sulfates,alkylsulfonates, alkyl ether sulfates, alkylphenol ether sulfates, alkylpolyglycol ether phosphates, alkyldiphenyl ether sulfonates,polyarylphenyl ether phosphates, alkyl sulfosuccinates, olefinsulfonates, paraffin sulfonates, petroleum sulfonates, taurides,sarcosides, fatty acids, alkylnaphthalenesulfonic acids ornaphthalenesulfonic acids, including their alkali metal, alkaline earthmetal, ammonium and amine salts. Examples of anionic protective colloidsare lignosulfonic acids, condensation products of sulfonatednaphthalenes with formaldehyde or with formaldehyde and phenol and, ifappropriate, urea, and also condensation products from phenolsulfonicacid, formaldehyde and urea, lignin sulfite waste liquor andlignosulfonates, and also polycarboxylates, such as polyacrylates,maleic anhydride/olefin copolymers (e.g. Sokalan® CP9, BASF), and alsothe alkali metal, alkaline earth metal, ammonium and amine salts of theabove-mentioned protective colloids.

Nonionic emulsifiers are, for example, alkylphenol alkoxylates, alcoholalkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fattyacid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty acidamide alkoxylates, fatty acid polydiethanolamides, lanolin ethoxylates,fatty acid polyglycol esters, isotridecyl alcohol, fatty acid amides,methylcellulose, fatty acid esters, silicone oils, alkylpolyglycosidesand glycerol fatty acid esters. Examples of nonionic protective colloidsare polyethylene glycol, polypropylene glycol, polyethyleneglycol/polypropylene glycol block copolymers, polyethylene glycol alkylethers, polypropylene glycol alkyl ethers, polyethyleneglycol/polypropylene glycol ether block copolymers, and their mixtures.

Examples of cationic emulsifiers are quaternary ammonium salts, e.g.trimethyl- and triethyl(C₆-C₃₀-alkyl)ammonium salts, such ascocotrimethylammonium salts and trimethylcetylammonium salts, dimethyl-and diethyldi(C₄-C₂₀-alkyl)ammonium salts, such asdidecyldimethylammonium salts and dicocodimethylammonium salts, methyl-and ethyltri(C₄-C₂₀-alkyl)ammonium salts, such as methyltrioctylammoniumsalts, (C₁-C₂₀-alkyl)di(C₁-C₄-alkyl)benzylammonium salts, such astriethylbenzylammonium salts and cocobenzyldimethylammonium salts,methyl- and ethyldi(C₄-C₂₀-alkyl)poly(oxyethyl)ammonium salts, e.g.didecylmethylpoly(oxyethyl)ammonium salts, N—(C₆-C₂₀-alkyl)pyridiniumsalts, e.g. N-laurylpyridinium salts, N-methyl- andN-ethyl-N—(C₆-C₂₀-alkyl)morpholinium salts, and N-methyl- andN-ethyl-N′—(C₆-C₂₀-alkyl)imidazolinium salts, in particular the halides,borates, carbonates, formates, acetates, propionates,hydrogencarbonates, sulfates and methyl sulfates.

Examples of cationic protective colloids are homo- and copolymers of theabovementioned monomers M2c with a content of monomers M2c of at least20% by weight, in particular at least 30% by weight of monomers M2c, forexample homopolymers of N-vinyl-N-methylimidazolinium salts or ofN-alkylvinylpyridinium salts and copolymers of these monomers withneutral monomers M2b which are preferably miscible with water.

Zwitterionic emulsifiers are those with betaine structures. Suchsubstances are known to a person skilled in the art and can be takenfrom the relevant state of the art (see, for example, R. Heusch, inUllmann's Encyclopedia of Industrial Chemistry, 5th ed., on CD-ROM,Wiley-VCH, 1997, “Emulsions”, chapter 7, Table 4).

The compositions according to the invention usually comprise at leastone emulsifier, preferably at least one ionic emulsifier and, ifappropriate, one or more nonionic emulsifiers. With regard to theapplication in wood preservation, it has proved worthwhile for thecompositions according to the invention to comprise at least onecationic emulsifier, in particular if no monomers M2c are used toprepare the polymer.

The amount of emulsifier usually ranges from 0.1 to 15% by weight, inparticular from 0.2 to 12% by weight and particularly preferably from0.7 to 10% by weight, based on the monomers M or on the polymer P. Theamount of ionic emulsifier is preferably 0.3 to 10% by weight and inparticular 0.5 to 8% by weight, based on the monomers M constituting thepolymer. The amount of nonionic emulsifier preferably ranges from 0.2 to12% by weight, in particular from 0.5 to 10% by weight, based on themonomers M constituting the polymer.

The preparation of the aqueous compositions according to the inventioncomprises a radical aqueous emulsion polymerization of an oil-in-wateremulsion of the monomers M, in which the monomer droplets of theemulsion comprise at least one fungicidal active substance and, ifappropriate, an insecticidal active substance. The polymerization iscarried out analogously to a conventional emulsion polymerization, withthe difference that the monomer emulsion to be polymerized comprises theactive substance dissolved in the monomer droplets.

The oil-in-water emulsion of the active substance/monomer solution canbe prepared in situ by addition of a solution of the active substance inthe monomers M to be polymerized in the polymerization vessel placedunder polymerization conditions. However, preferably, the activesubstance will be dissolved in the monomers M and the monomer solutionthus obtained will be converted to an aqueous monomer emulsion, beforethe monomer/active substance emulsion thus obtained is fed to thepolymerization reaction.

The polymerization is generally carried out according to a “monomer feedprocess”, i.e. the greater part, preferably at least 70% and inparticular at least 90%, of the solution of the active substance in themonomers M or the greater part, preferably at least 70% and inparticular at least 90%, of the monomer/active substance emulsion is fedto the polymerization vessel in the course of the polymerizationreaction. The addition of the monomer/active substance solution oremulsion is preferably carried out over a period of at least 0.5 h,preferably at least 1 h, e.g. 1 to 10 h and in particular 2 to 5 h. Theaddition of the monomer/active substance solution or emulsion can becarried out with a constant or variable addition rate, e.g. in intervalswith a constant addition rate or with a variable addition rate orcontinuously with a variable addition rate. The composition of themonomer/active substance solution or emulsion can remain constant duringthe addition or can be changed, it being possible for changes to be madeboth with regard to the monomer composition and with regard to the typeof active substance or the concentration of the active substance.

In a preferred embodiment of the invention, the monomer composition ischanged in the course of the monomer addition in such a way that polymerregions with a different glass transition temperature are obtained inthe polymer particles. This is achieved by a “step polymerization”. Forthis, first, a first monomer/active substance solution or emulsion, themonomer composition of which corresponds to a glass transitiontemperature T_(g) ¹, is polymerized in a first step and subsequently asecond monomer/active substance solution or emulsion, the monomercomposition of which corresponds to a glass transition temperature T_(g)², is provided for this (2nd step) and, if appropriate, subsequentthereto, successively one or more additional monomer/active substancesolutions or emulsions, the monomer composition of which corresponds ineach case to a glass transition temperature T_(g) ^(n), n being therespective step, is/are provided for this. The respective glasstransition temperatures in polymers obtained in successivepolymerization steps preferably differ by at least 10 K, in particularby at least 20 K and particularly preferably by at least 30 K, e.g. 30 Kto 200 K, in particular 40 K to 160 K. Generally, the monomer amountpolymerized in a monomer amount will come to at least 5% by weight,preferably at least 10% by weight, e.g. 5 to 95% by weight, inparticular 10 to 90% by weight, in a 2-step polymerization and 5 to 90or 5 to 85% by weight, in particular 10 to 80% by weight, in apolymerization with three or more steps.

It has proved to be advantageous, for the preparation of the activesubstance composition according to the invention and for the propertiesof the active substance composition, for the emulsion polymerization tobe carried out in the presence of a seed polymer (seed latex). In thisconnection, it is a finely divided polymer latex, the average particlesize of which is usually not more than 100 nm, in particular not morethan 80 nm and particularly preferably not more than 50 nm. The monomersconstituting the seed latex are preferably to at least 90% by weight, inparticular to at least 95% by weight and frequently to more than 99% byweight selected from the monomers M1, the seed latex also being able tocomprise, for the stabilization, small amounts, e.g. 0.1 to 10% byweight, in particular 0.1 to 5% by weight and especially 0.1 to 1% byweight, thereof different monomers M2, e.g. monomers M2a. The seed latexfrequently exhibits a glass transition temperature of at least 10, inparticular of at least 50 and frequently of at least 80° C. The amountof seed latex is usually 0.01 to 5% by weight, in particular 0.1 to 4%by weight, based on the monomers M1 to be polymerized. Preferably, thebulk, and in particular all, of the seed latex is found, at thebeginning of the polymerization, completely in the reaction vessel. Theseed latex can also be generated in situ in the polymerization vessel byradical emulsion polymerization of the monomers which form the seedlatex, the monomers which form the seed latex being selected from theabovementioned monomers M1 and M2 and in particular to at least 90% byweight from the monomers M1. The desired particle size of the seed latexcan be controlled in a way known per se via the ratio of monomer toemulsifier.

The initiators suitable for the emulsion polymerization according to theinvention are the polymerization initiators suitable for andconventionally used for an emulsion polymerization which initiate aradical polymerization of the monomers M. These include azo compounds,such as 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methyl-butyronitrile),2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],1,1′-azobis(1-cyclohexanecarbonitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride and2,2′-azobis(2-amidinopropane) dihydrochloride, organic or inorganicperoxides, such as diacetyl peroxide, di(tert-butyl) peroxide, diamylperoxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide,dibenzoyl peroxide, bis(o-toluoyl) peroxide, succinyl peroxide,tert-butyl peracetate, tert-butyl permaleate, tert-butyl perisobutyrate,tert-butyl perpivalate, tert-butyl peroctoate, tert-butylperneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butylhydroperoxide, cumene hydroperoxide, tert-butyl peroxy(2-ethylhexanoate)and diisopropyl peroxydicarbamate, salts of peroxydisulfuric acid andredox initiator systems.

Use is preferably made of water-soluble initiators, e.g. cationic azocompounds, such as azobis(dimethylamidinopropane), salts ofperoxydisulfuric acid, in particular a sodium, potassium or ammoniumsalt, or a redox initiator system, which a salt of peroxydisulfuricacid, hydrogen peroxide or an organic peroxide, such as tert-butylhydroperoxide, as oxidizing agent. As reducing agent, they preferablycomprise a sulfur compound which is selected in particular from sodiumhydrogensulfite, sodium hydroxymethanesulfinate and the hydrogensulfiteadduct of acetone. Additional suitable reducing agents arephosphorus-comprising compounds, such as phosphorous acid,hypophosphites and phosphinates, and also hydrazine or hydrazine hydrateand ascorbic acid. Redox initiator systems can furthermore comprise theaddition of small amounts of redox metal salts, such as iron salts,vanadium salts, copper salts, chromium salts or manganese salts, suchas, for example, the redox initiator system ascorbic acid/iron(II)sulfate/sodium peroxydisulfate.

The initiator is generally used in an amount of 0.02 to 2% by weight andin particular 0.05 to 1.5% by weight, based on the amount of themonomers M. The optimal amount of initiator naturally depends on theinitiator system used and can be determined by a person skilled in theart by routine experiments. The initiator can be partially or completelyintroduced into the reaction vessel. Preferably, the bulk of theinitiator, in particular at least 80%, e.g. 80 to 99.5%, of theinitiator, is provided to the polymerization reactor in the course ofthe polymerization.

The pressure and temperature are of secondary importance for thepreparation of the active substance compositions according to theinvention. The temperature naturally depends on the initiator systemused and an optimal polymerization temperature can be determined by aperson skilled in the art through routine experiments. Thepolymerization temperature usually ranges from 20 to 110° C., frequentlyfrom 50 to 95° C. The polymerization is usually carried out at standardpressure or ambient pressure. However, it can also be carried out underincreased pressure, e.g. up to 3 bar, or under slightly reducedpressure, e.g. >800 mbar.

The emulsifiers and protective colloids conventionally used for emulsionpolymerization which have already been mentioned above as constituentsof the active substance formulations according to the invention aresuitable as surface-active substances. The amounts of surface-activesubstances conventionally used for an emulsion polymerization generallylie in the ranges given above, so that all or a portion of thesurface-active substances in the compositions according to the inventionis supplied via the emulsion polymerization. However, it is alsopossible to use, in the emulsion polymerization, only a portion, e.g. 10to 90% by weight, in particular 20 to 80% by weight, of thesurface-active substances present in the composition according to theinvention and to add the remaining amounts of surface-active substancesubsequent to the emulsion polymerization, before or after an optionaldeodorization of the emulsion polymerization (subsequentsaponification).

The molecular weight of the polymers can obviously be adjusted byaddition of a small amount of regulators, e.g. 0.01 to 2% by weight,based on the monomers M which are being polymerized. In particular,organic thio compounds and also allyl alcohols and aldehydes aresuitable as regulator.

Subsequent to the actual polymerization reaction, it may be necessary tosubstantially free the aqueous polymer dispersions according to theinvention from odorous substances, such as residual monomers and othervolatile organic constituents. In a way known per se, this can beachieved physically by distillative removal (in particular via steamdistillation) or by stripping with an inert gas. Furthermore, theresidual monomers can be lowered chemically by radicalpostpolymerization, in particular under the effects of redox initiatorsystems, such as are listed, e.g., in DE-A 44 35 423, DE-A 44 19 518 andDE-A 44 35 422. The postpolymerization is preferably carried out with aredox initiator system composed of at least one organic peroxide and oneorganic sulfite.

After the end of the polymerization, the polymer dispersions used arefrequently, before their use according to the invention, adjusted to analkaline value, preferably to pH values ranging from 7 to 10. Ammonia ororganic amines, and also, preferably, hydroxides, such as sodiumhydroxide, potassium hydroxide or calcium hydroxide, can be used for theneutralization.

In this way, stable aqueous polymer dispersions are obtained whichcomprise, in the polymer particles of the dispersion, at least onefungicidal active substance, and, if appropriate, one or moreinsecticidal active substances. In addition, the dispersions thusobtained comprise the abovementioned surface-active substances. Theactive substance preparations thus obtained are characterized by a highstability and a low content of volatile organic compounds, which usuallycome to not more than 1% by weight, frequently not more than 0.1% byweight and in particular not more than 500 ppm, based on the totalweight of the composition. Volatile compounds are, here andsubsequently, all organic compounds which exhibit a boiling point ofless than 200° C. at standard pressure.

The solids content of the compositions according to the invention isdetermined to a first approximation by the active substance and thepolymer and generally ranges from 10 to 60% by weight and in particularfrom 20 to 50% by weight.

The active substance compositions thus obtainable can be used directlyas such or after diluting. In addition, the compositions according tothe invention can also comprise conventional additives, e.g.viscosity-modifying additives (thickeners), antifoam agents,bactericides and antifreeze agents.

Suitable thickeners are compounds which confer a pseudoplastic flowbehavior on the formulation, i.e. high viscosity at rest and lowviscosity in the agitated state. Mention may be made, in thisconnection, for example, of polysaccharides or organic layered minerals,such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol® 23 (Rhône-Poulenc)or Veegum® (R.T. Vanderbilt), or Attaclay® (Engelhardt), Xanthan Gum®preferably being used.

Silicone emulsions (such as, e.g., Silicone® SRE, from Wacker, orRhodorsil® from Rhodia), long-chain alcohols, fatty acids, fluoroorganiccompounds and their mixtures, for example, come into consideration asantifoam agents suitable for the dispersions according to the invention.

Bactericides can be added to stabilize the compositions according to theinvention from infection by microorganisms, Suitable bactericides are,for example, Proxel® from Avecia (or Arch) or Acticide® RS from ThorChemie and Kathon® MK from Röhm & Haas.

Suitable antifreeze agents are organic polyols, e.g. ethylene glycol,propylene glycol or glycerol. These are generally used in amounts of notmore than 10% by weight, based on the total weight of the activesubstance composition.

If appropriate, the active substance compositions according to theinvention can, to regulate the pH, comprise 1 to 5% by weight of buffer,based on the total amounts of the formulation prepared, the amounts andthe type of the buffer used depending on the chemical properties of theactive substance or substances. Examples of buffers are alkali metalsalts of weak inorganic or organic acids, such as, e.g., phosphoricacid, boric acid, acetic acid, propionic acid, citric acid, fumaricacid, tartaric acid, oxalic acid and succinic acid.

In addition, the aqueous compositions according to the invention can beformulated with conventional binders, for example aqueous polymerdispersions or water-soluble resins, for example water-soluble alkydresins, or with waxes.

For use in the protection of cellulose-comprising materials, inparticular in wood preservation, the aqueous active substancecompositions according to the invention can also be formulated withconventional water-soluble wood preservatives, in particular with theiraqueous solutions, in order to improve the overall effectiveness againstwood-destroying organisms. In this connection, these are, for example,aqueous preparations of conventional wood-protecting salts, for exampleof salts based on boric acid and alkali metal borates, salts based onquaternary ammonium compounds, e.g. trimethyl- andtriethyl(C₆-C₃₀-alkyl)ammonium salts, such as cocotrimethylammoniumchloride or trimethylcetylammonium salts, dimethyl- anddiethyldi(C₄-C₂₀-alkyl)ammonium salts, such as didecyldimethylammoniumchloride, didecyldimethylammonium bromide or dicocodimethylammoniumchloride, (C₁-C₂₀-alkyl)di(C₁-C₄-alkyl)benzylammonium salts, such ascocobenzyldimethylammonium chloride, or methyl- andethyldi(C₄-C₂₀-alkyl)poly(oxyethyl)ammonium salts, e.g.didecylmethylpoly(oxyethyl)ammonium chloride and propionate, and alsothe borates, carbonates, formates, acetates, hydrogencarbonates,sulfates and methyl sulfates, or aqueous preparations of copper-aminecomplexes, in particular aqueous preparations of salts comprising copperethanolamine, for example Cu-HDO. Obviously, the aqueous activesubstance preparations according to the invention can also be formulatedwith other aqueous fungicidal and insecticidal active substancecompositions, for example with conventional emulsion concentrates,suspension concentrates or suspoemulsion concentrates of theabovementioned active substances, e.g. of the abovementioned fungicidesfrom the group of the azoles and of the strobilurins or of theabovementioned insecticides, or with the microemulsions, mentioned atthe start, of the abovementioned fungicides and insecticides. By mixingthe aqueous active substance composition according to the invention withconventional aqueous preparations of the abovementioned activesubstances, a broadening in the spectrum of activity is first obtained,if the conventional preparation comprises a different active substancefrom the aqueous active substance composition according to theinvention. Secondly, the advantages of the active substance compositionsaccording to the invention are not lost by formulating with conventionalaqueous active substance preparations, in particular the improvedadhesion to cellulose-comprising materials and especially to wood.Consequently, the application properties of a conventional aqueousactive substance preparation can be improved by formulating with anaqueous active substance composition according to the invention of thesame active substance.

There are a number of advantages to the active substance compositionsaccording to the invention. First, these are stable aqueous formulationsof fungicidal active substances which are insoluble in water or aresoluble in water only to a slight extent. In particular, the phaseseparation problems observed in conventional formulations and in micro-or nanodispersions of the active substances are not observed andsettling of the active substance is not observed, even when drasticconditions are employed, such as occur in the processes employed forimpregnating wood with fungicidal active substances. The content ofvolatile organic compounds is with conventional additivating lower thanwith comparable conventional formulations and, in comparison to micro-or nanodispersions of active substances, the proportion of emulsifier issimultaneously lower, based on the active substance used. The activesubstance is leached from the treated material, under the effect ofwater, to a markedly lesser extent in comparison with otherformulations. Furthermore, interactions of the active substances withother formulation constituents or additional active substances, such asfrequently occur with a conventional formulation, are not observed.Furthermore, the decomposition of the active substances by the effectsof the substrate or environment, such as pH value of the medium or UVradiation, is slowed down or even completely halted. Surprisingly, areduced effectiveness of the active substance through the incorporationin a polymer matrix is not observed.

The present invention also relates to a process for the protection ofcellulose-comprising materials, in particular wood, from infection byharmful fungi, in particular from infection by the abovementionedwood-destroying fungi, in which the cellulose-comprising material, inparticular wood, is treated with a composition according to theinvention.

Cellulose-comprising materials are, in addition to wood and downstreamproducts, e.g. wood blanks, plywood, chipboard, MDF panels or OSBpanels, also pulps and intermediates in the manufacture of paper,fabrics based on cellulose, such as cotton, materials based on woodyannuals, for example molded articles formed from rape shavings, bargassepanels, straw panels, and the like. The cellulose-comprising materialsfurthermore include articles formed from cellulose-comprising fibermaterials, such as fabrics, formed fabrics, paper, board,heat-insulating materials, ropes, cables, and the like. Suitable fibermaterials for the process according to the invention comprise textilefibers, such as flax, linen, hemp, jute, cotton and ramie, paper fibers,such as flax, linen or hemp, bamboo fibers, paper mulberry andlignocellulose fibers, and also nettle fiber, manila hemp, sisal, kenafand coconut fiber.

The treatment can be carried out in a way known per se, depending on thetype of substrate, by spraying, painting, dipping or impregnating thesubstrate with an undiluted active substance composition according tothe invention or an active substance composition according to theinvention diluted with water or by flooding the substrate in anundiluted aqueous active substance composition according to theinvention or an aqueous active substance composition according to theinvention diluted with water. The compositions according to theinvention can also be present in the manufacture of thecellulose-comprising material, for example as binder or as sizing agent.

If the substrate according to the invention is wood, use may be made ofthe processes conventional in wood preservation, such as are known, forexample, from Ullmann's Encyclopedia of Industrial Chemistry, Woodpreservation, 5th edition on CD-ROM, Wiley VCH, Weinheim, 1997, chapter7. These include in particular processes for impregnating the wood withthe help of pressure differences, e.g. the vacuum-pressure process anddouble vacuum impregnation.

The treatment of such materials with the active substance compositionsaccording to the invention can be carried out according to the processesconventional for this and will be adapted in a way known per se to thetechnical realities in each case. The application concentration and theincorporation depend in this connection on the degree of danger of thematerial and on the respective treatment process and usually range from0.05 mg to 10 g of active substance per kg of material.

The undiluted composition comprising the active substance is frequentlyused in wood downstream products and cellulose-comprising materials, forexample together with the binder used, as cobinder. Obviously, separatetreatment during or after the manufacture, for example the sizing, isalso possible.

In addition to the cellulose-based materials mentioned, the aqueousactive substance composition according to the invention can also be usedin other areas of material protection from infection by harmful fungiand, if appropriate, from infection by animal pests. For example, skin,fur or leather can be effectively protected, with the aqueouscompositions according to the invention, from infection bymicroorganisms, in particular from infection by the abovementionedharmful fungi, and animal pests. In addition, the aqueous compositionsaccording to the invention can also be used as antifouling paints, forexample in shipbuilding, or as algicidal paint systems for facades androofing tiles, depending on the active substance present therein in eachcase. In addition, the compositions according to the invention can beused as in-can and film preservatives.

The following examples should clarify the invention, without, however,limiting it:

The viscosities given were determined in a Brookfield rotary viscometerat 23° C. in accordance with ISO 2555.

The particle sizes given were determined by quasielastic lightscattering according to the methods described above in diluteddispersions (0.01 to 0.1% by weight). The average diameter, determinedby the cumulant analysis of the autocorrelation function measured, isgiven.

The glass transition temperature was determined in accordance with ASTMD 3418 using differential scanning calorimetry.

I. Preparation of the Active Substance Composition EXAMPLE 1a AqueousPolymer Dispersion with 3% by Weight of Active Substance, Dispersion D1

300 g of deionized water and 13.6 g of a 33% by weight aqueouspolystyrene dispersion (average particle size 30 nm) were introducedinto a reaction vessel equipped with a stirrer, the vessel was flushedwith nitrogen and was then heated to 75° C. Beginning simultaneously,feed 1 was added within 3 h and feed 2 was added within 3.15 h, withstirring and while maintaining the temperature. After the end of theaddition of feed 2, the temperature was maintained for a further 30 minand then 3.0 g of a 25% by weight aqueous ammonia solution were added.Subsequently, for the purposes of chemical deodorization, feed 3 andfeed 4 were added within 90 min while maintaining the temperature andthen the reaction mixture was cooled down to ambient temperature. Feed 5was then added in one portion and the reaction mixture was stirred for10 min, then adjusted to a pH value of 7 to 7.5 with ammonia and thenfiltered through a mesh with a mesh size of 125 μm.

The dispersion obtained had a solids content of 38.7% by weight and aviscosity of 30 mPa·s. The glass transition temperature of the polymerwas +16° C. The average particle size, determined by means of lightscattering, was 146 nm.

-   -   Feed 1:    -   400.0 g of deionized water    -   25.7 g of a 28% by weight solution of an anionic emulsifier E1¹)    -   21.0 g of a 28% by weight solution of a nonionic emulsifier E2²)    -   7.8 g of acrylic acid    -   292.0 g of styrene    -   237.0 g of n-butyl acrylate    -   60.0 g of ethyl acrylate    -   3.0 g of acrylamide    -   18.0 g of epoxiconazole    -   Feed 2:    -   100 g of deionized water    -   2.4 g of sodium peroxodisulfate    -   Feed 3:    -   22.0 g of deionized water    -   2.6 g of t-butyl hydroperoxide (70% by weight)    -   Feed 4:    -   25.0 g of deionized water    -   1.7 g of sodium hydroxymethanesulfinate    -   Feed 5:    -   37.0 g of deionized water    -   30.0 g of emulsifier solution E2    -   1) sodium lauryl sulfate    -   2) C₁₆/C₁₈ fatty alcohol ethoxylate with on average 18 ethylene        oxide units per molecule

EXAMPLE 1b Aqueous Polymer Dispersion with 2% by Weight of FungicidalActive Substance and 1% by Weight of Insecticidal Active Substance,Dispersion D2

The preparation was carried out analogously to the procedure of example1a, feed 1 having the following composition:

-   -   Feed 1:    -   400.0 g of deionized water    -   25.7 g of a 28% by weight solution of an anionic emulsifier E1¹)    -   21.0 g of a 28% by weight solution of a nonionic emulsifier E2²    -   7.8 g of acrylic acid    -   322.0 g of styrene    -   177.0 g of n-butyl acrylate    -   60.0 g of ethyl acrylate    -   30.0 g of acrylonitrile    -   3.0 g of acrylamide    -   12.0 g of epoxiconazole    -   6.0 g of chlorfenapyr

The dispersion obtained had a solids content of 39% by weight and aviscosity of 45 mPa·s. The glass transition temperature of the polymerwas 31° C. The average particle size, determined by means of lightscattering, was 151 nm.

EXAMPLE 2 Step Polymers with Different Active Substances, Dispersions D3to D8 General Procedure:

183 g of water and 75.8 g of an aqueous polystyrene dispersion (33% byweight, average particle diameter 30 nm) were introduced into a reactionvessel, the vessel was flushed with nitrogen and was heated to 85° C.25% by weight of a solution of 1.5 g of sodium peroxodisulfate in 21.4 gof water (feed 4) were added hereto while maintaining the temperature.After 10 min, beginning simultaneously, the addition of feed 1 and theaddition of the remaining amount of feed 4 were commenced. Feed 1 wasadded within 90 min while maintaining the temperature, feed 4 within 255min. After the end of the addition of feed 1, the temperature wasmaintained for 30 min, then feed 2 was added within 60 min, thetemperature was maintained for a further 45 min and then feed 3 wasadded within 30 min while maintaining the temperature. After the end ofthe addition of feed 3, the temperature was maintained for a further 30min and then the reaction mixture was cooled to ambient temperature.

-   -   Feed 1:    -   220.1 g of water    -   220.8 g of styrene    -   1.6 g of allyl methacrylate    -   11.1 g of emulsifier solution E3    -   x g of active substance (see table 1)    -   Feed 2:    -   135.6 g of water    -   180.4 g of n-butyl acrylate    -   2.1 g of allyl methacrylate    -   7.2 g of emulsifier solution E3    -   y g of active substance (see table 1)    -   Feed 3:    -   92.5 g of water    -   19.7 g of styrene    -   75.5 g of methyl methacrylate    -   1.7 g of emulsifier solution E3    -   z g of active substance (see table 1)

Emulsifier solution E3: 45% by weight aqueous solution of a sodium saltof (C₁₆-alkyl)-diphenyl ether sulfonic acid

TABLE 1 Dispersion Active substance x [g] y [g] z [g] D3 Metconazole26.4 14.4 12.0 D4 Cyproconazole 21.6 10.8 10.8 D5 Epoxiconazole 30.0 6.06.0 D6 Tebuconazole 15.0 18.0 — D7 IPBC¹⁾ 21.0 4.2 6.0 D8Epoxiconazole + 4.0 4.0 4.0 Chlorfenapyr 2.0 2.0 2.0 ¹⁾IPBC =3-iodo-2-propyl butylcarbamate.

The dispersions obtained had a solids content of 45% by weight and aviscosity of 115 mPa·s. The polymer showed 2 glass transitiontemperatures at −31 and +99° C. determined by means of DSC. The averageparticle size, determined by means of light scattering, was 95 to 105nm.

EXAMPLE 3 Cationic Dispersions D9-D13 with Different Active SubstancesGeneral Preparation Procedure:

465 g of deionized water, 5% by weight of feed 1 and 10% by weight offeed 2 were heated to 80° C. After 10 min, the addition of the remainingamounts of feed 1 and feed 2 was commenced. The feed time was 3.5 h.After the end of the addition of the feeds, the mixture was maintainedat 80° C. for a further 30 min and was cooled down to ambienttemperature.

-   -   Feed 1:    -   496.1 g of deionized water    -   7.6 g of sulfuric acid (50% by weight)    -   361.0 g of methyl methacrylate    -   19.0 g of dimethylaminoethyl methacrylate    -   57.0 g of emulsifier solution E4    -   x g of active substance (see table 2)    -   Feed 2:    -   Solution of 1.5 g of 2,2′-azobis(N,N′-dimethylisobutyramidine)        in 63.3 g of deionized water

Emulsifier solution E4: 40% by weight aqueous solution of a cationicemulsifier obtained by successive ethoxylation of stearylamine with 4-5mol of ethylene oxide and subsequent quaternization with dimethylsulfate.

TABLE 2 Dispersion Active substance x [g] D9 Metconazole 61.8 D10Cyproconazole 42.9 D11 Epoxiconazole 0.4 D12 Tebuconazole 19.0 D13 IPBC18.2

The dispersion obtained had a solids content of 29.5% by weight and aviscosity of 100 mPa·s. The polymer showed a glass transitiontemperature at 87° C. determined by means of DSC. The average particlesize, determined by means of light scattering, was 157 to 175 nm.

EXAMPLE 4 Cationic Dispersions D14-D18 with Different Active SubstancesGeneral Preparation Procedure:

465 g of deionized water, feed 1 and 10% by weight of feed 2 were heatedto 80° C. After 10 min, the addition of the remaining amount of feed 2and of feed 3 was begun. The feed time of feed 2 and feed was 3.5 h.After the end of the addition of the feeds, the mixture was maintainedat 80° C. for a further 30 min and was then cooled down to ambienttemperature.

-   -   Feed 1:    -   46.1 g of deionized water    -   38.0 g of styrene    -   7.6 g of 3-(N,N-dimethylamino)propylmethacrylamide    -   14.2 g of emulsifier solution E4 (see above)    -   Feed 2:    -   Solution of 1.5 g of 2,2′-azobis(N,N′-dimethylisobutyramidine)        in 63.3 g of deionized water    -   Feed 3:    -   450.1 g of deionized water    -   7.6 g of acrylic acid    -   270.0 g of methyl methacrylate    -   57.0 g of dimethylaminoethyl methacrylate    -   42.8 g of emulsifier solution E4 (see above)    -   x g of active substance (see table 3)

TABLE 3 Dispersion Active substance x [g] D14 Metconazole 61.8 D15Cyproconazole 42.9 D16 Epoxiconazole 0.4 D17 Tebuconazole 19.0 D18IPBC¹⁾ 18.2

The dispersion obtained had a solids content of 29.8% by weight and aviscosity of 105 mPa·s. The polymer showed a glass transitiontemperature at 110° C. determined by means of DSC. The average particlesize, determined by means of light scattering, was 155 to 175 nm.

II. Application investigation:

The limits of the effectiveness of the compositions according to theinvention with regard to wood-destroying basidiomycetes were determinedon wood test specimens of Pinus spp. (southern yellow pine) with thedimensions 40×15×4 mm³. The test method on comminuted wood testspecimens, known as the Bravery test, is closely based on EN 113 and isused to determine the preventive effect of wood preservatives againstwood-destroying fungi (see in this connection A. F. Bravery, Intern.Res. Group Wood Pres., Doc. No. IRGNVP/2113, 5S., Stockholm, 1978). Thewood test specimens impregnated with the composition according to theinvention were tested without or with the constraint of leachingaccording to EN 84. The investigation was carried out with 6 differentactive substance concentrations ranging from 0.4 to 4% by weight ofactive substance (with epoxiconazole) or 0.63 to 6.3% by weight ofactive substance (with tebuconazole) and each time 5 parallel testspecimens per active substance concentration and test fungus. Coniophoraputeana BAM Ebw. 15 and Poria placenta FPRL 280 were used as test fungi.The destruction of the wood caused by fungal infection was registered bythe loss in weight of the test woods, which was determined after 6weeks. If the loss in weight is less than 3% by weight, based on thestarting dry weight of the test sample, the protection of the woodachieved by the preservative at a particular active substanceconcentration is regarded as satisfactory. The concentration limit ofthe effectiveness is given in two concentrations. The lowerconcentration gives the value at which the wood is no longersatisfactorily protected and the higher concentration corresponds to theminimum concentration with which complete protection is achieved.

A dispersion with an active substance content of 5.52% by weight ofepoxiconazole (based on the solids content, or 2.4% by weight, based onthe dispersion), a solids content of 43.7% by weight and an averageparticle size of 107 nm, prepared according to the procedure in example2, and a dispersion with an active substance content of 4.69% by weightof tebuconazole (based on the solids content, or 2.05% by weight, basedon the dispersion), a solids content of 43.8% by weight and an averageparticle size of 98 nm, prepared according to the procedure in example2, were tested.

The limits of the effectiveness are represented in table 4. Forcomparison, the values determined for a solution of the active substancein acetone are given.

TABLE 4 Limits of the effectiveness [kg/m³] Test fungus Without leachingWith leaching (EN 84) Dispersion with epoxiconazole CP <0.066 <0.066 PP<0.066 <0.066 Solution of epoxiconazole CP <0.19 0.11-0.16 PP <0.190.11-0.18 Dispersion with tebuconazole CP <0.092 <0.089 PP 0.091-0.143<0.092 Solution of tebuconazole CP <0.052 <0.054 PP 0.102-0.1530.095-0.152

In practice, the upper value after leaching in particular is decisivefor the assessment of a wood preservative. The results represented intable 4 prove that the active substance compositions according to theinvention show an effectiveness against wood-destroying fungi which isat least comparable to, in the case of epoxiconazole even better than,that of formulations in organic solvents.

Wood test specimens which, for control purposes, were treated only witha dispersion free of active substance with otherwise an identicalcomposition showed, under test conditions, serious damage to the woodsubstance by fungal infection which was only slightly less than withuntreated wood test samples.

1. A process for the protection of cellulose-comprising materials frominfection by microorganisms comprising the treatment of thecellulose-comprising material with an aqueous active substancecomposition, comprising a) at least one fungicidal organic activesubstance with a solubility in water of less than 1 g/l at 25° C./1013mbar, and b) a finely-divided polymer with an average particle size,determined by dynamic light scattering, of 10 to 250 nm, in which thepolymer particles comprise the active substance, the polymer having aglass transition temperature of at least 10° C. and being formed fromethylenically unsaturated monomers M consisting of: from 70 to 99.5% byweight, based on the total amount of the monomers M, of at least oneneutral monoethylenically unsaturated monomer M1 with a solubility inwater of not more than 30 g/l at 25° C., which is selected from styreneand esters of monoethylenically unsaturated mono- or dicarboxylic acidswith C₁-C₁₀-alkanols or C₅-C₈-cycloalkanols, and from 0.50 to 30% byweight, based on the total amount of the monomers M, of at least oneethylenically unsaturated monomers M2, which is selected from:monoethylenically unsaturated momomers M2a exhibiting at least one acidgroup or at least one anionic group, the amount of monomers M2a beingnot more than 20% by weight, based on the total amount of the monomersM; monoethylenically unsaturated neutral monomers M2b exhibiting asolubility in water of at least 50 g/l at 25° C., the amount of monomersM2b being not more than 10% by weight, based on the total amount of themonomers M; and monoethylenically unsaturated monomers M2c exhibiting atleast one cationic group and/or at least one group which can beprotonated in the aqueous medium, the amount of monomers M2c being notmore than 20% by weight, based on the total amount of the monomers M;and not more than 2% by weight, based on the total amount of themonomers M, of monomers having two or more nonconjugated ethylenicallyunsaturated double bonds, wherein the aqueous active substancecomposition is obtained by a process comprising radical aqueous emulsionpolymerization of an oil-in-water emulsion of the monomers M, themonomer droplets of the oil-in-water emulsion to be polymerizedcomprising the fungicidal active substance in dissolved form.
 2. Theprocess according to claim 1, wherein the cellulose-comprising materialis wood.